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Title: Transition metal dissolution, ion migration, electrocatalytic reduction and capacity loss in Lithium-ion full cells

Abstract

Continuous operation of full cells with layered transition metal (TM) oxide positive electrodes (NCM523) leads to dissolution of TM ions and their migration and incorporation into the solid electrolyte interphase (SEI) of the graphite-based negative electrode. These processes correlate with cell capacity fade and accelerate markedly as the upper cutoff voltage (UCV) exceeds 4.30 V. At voltages ≥ 4.4 V there is enhanced fracture of the oxide during cycling that creates new surfaces and causes increased solvent oxidation and TM dissolution. Despite this deterioration, cell capacity fade still mainly results from lithium loss in the negative electrode SEI. Among TMs, Mn content in the SEI shows a better correlation with cell capacity loss than Co and Ni contents. As Mn ions become incorporated into the SEI, the kinetics of lithium trapping change from power to linear at the higher UCVs, indicating a large effect of these ions on SEI growth and implicating (electro)catalytic reactions. Lastly, we estimate that each Mn II ion deposited in the SEI causes trapping of ~10 2 additional Li + ions thereby hastening the depletion of cyclable lithium ions. Using these results, we sketch a mechanism for cell capacity fade, emphasizing the conceptual picture over themore » chemical detail.« less

Authors:
 [1];  [1];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1339642
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 164; Journal Issue: 2; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; NCA; NCM523 oxide; SEI; electrochemistry; graphite; high voltage; layered oxides; manganese; nickel

Citation Formats

Gilbert, James A., Shkrob, Ilya A., and Abraham, Daniel P.. Transition metal dissolution, ion migration, electrocatalytic reduction and capacity loss in Lithium-ion full cells. United States: N. p., 2017. Web. doi:10.1149/2.1111702jes.
Gilbert, James A., Shkrob, Ilya A., & Abraham, Daniel P.. Transition metal dissolution, ion migration, electrocatalytic reduction and capacity loss in Lithium-ion full cells. United States. doi:10.1149/2.1111702jes.
Gilbert, James A., Shkrob, Ilya A., and Abraham, Daniel P.. Thu . "Transition metal dissolution, ion migration, electrocatalytic reduction and capacity loss in Lithium-ion full cells". United States. doi:10.1149/2.1111702jes. https://www.osti.gov/servlets/purl/1339642.
@article{osti_1339642,
title = {Transition metal dissolution, ion migration, electrocatalytic reduction and capacity loss in Lithium-ion full cells},
author = {Gilbert, James A. and Shkrob, Ilya A. and Abraham, Daniel P.},
abstractNote = {Continuous operation of full cells with layered transition metal (TM) oxide positive electrodes (NCM523) leads to dissolution of TM ions and their migration and incorporation into the solid electrolyte interphase (SEI) of the graphite-based negative electrode. These processes correlate with cell capacity fade and accelerate markedly as the upper cutoff voltage (UCV) exceeds 4.30 V. At voltages ≥ 4.4 V there is enhanced fracture of the oxide during cycling that creates new surfaces and causes increased solvent oxidation and TM dissolution. Despite this deterioration, cell capacity fade still mainly results from lithium loss in the negative electrode SEI. Among TMs, Mn content in the SEI shows a better correlation with cell capacity loss than Co and Ni contents. As Mn ions become incorporated into the SEI, the kinetics of lithium trapping change from power to linear at the higher UCVs, indicating a large effect of these ions on SEI growth and implicating (electro)catalytic reactions. Lastly, we estimate that each MnII ion deposited in the SEI causes trapping of ~102 additional Li+ ions thereby hastening the depletion of cyclable lithium ions. Using these results, we sketch a mechanism for cell capacity fade, emphasizing the conceptual picture over the chemical detail.},
doi = {10.1149/2.1111702jes},
journal = {Journal of the Electrochemical Society},
number = 2,
volume = 164,
place = {United States},
year = {Thu Jan 05 00:00:00 EST 2017},
month = {Thu Jan 05 00:00:00 EST 2017}
}

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Free Publicly Available Full Text
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Cited by: 12works
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  • Conductive transition metal oxides (perovskites, spinels and pyrochlores) are attractive as catalysts for the air electrode in alkaline rechargeable metal-air batteries and fuel cells. We have found that conductive carbon materials when added to transition metal oxides such as calcium-doped lanthanum cobalt oxide, nickel cobalt oxide and calcium-doped lanthanum manganese cobalt oxide increase the electrocatalytic activity of the oxide for oxygen reduction by a factor of five to ten. We have studied rotating ring-disk electrodes coated with (a) various mass ratios of carbon and transition metal oxide, (b) different types of carbon additives and (c) different types of transition metalmore » oxides. Our experiments and analysis establish that in such composite catalysts, carbon is the primary electro- catalyst for the two-electron electro-reduction of oxygen to hydroperoxide while the transition metal oxide decomposes the hydroperoxide to generate additional oxygen that enhances the observed current resulting in an apparent four-electron process. These findings are significant in that they change the way we interpret previous reports in the scientific literature on the electrocatalytic activity of various transition metal oxide- carbon composites for oxygen reduction, especially where carbon is assumed to be an additive that just enhances the electronic conductivity of the oxide catalyst. (C) 2013 The Electrochemical Society. All rights reserved.« less
  • This paper reviews the research activities on the mechanistic understanding and solutions to overcome the TM DMD process, from the earliest discoveries to the latest progress.
  • In lithium-ion cells, there are several different classes of capacity loss, both reversible and irreversible, that limit the cell's exploitable specific capacity and can lead to eventual cell failure. We attempt to clarify what is meant by capacity loss and cyclable lithium loss by defining these terms in the context of electrode state-of-charge restrictions. We define irreversible capacity loss as that associated with active material loss and define two types of reversible capacity loss associated with balanced and unbalanced side reactions. We also examine several methods of compensating for cyclable lithium loss associated with passive-film formation and calculate the effectmore » each has on a cell's specific energy. Preforming the negative electrode, adding cyclable lithium to the positive electrode, and introducing lithium powder into the negative electrode appear to be the most attractive methods in terms of specific energy, but practical constraints such as fabrication cost must be evaluated to determine which is superior.« less
  • UV/vis reflectance and electroreflectance experiments together with voltammetric and capacitance measurements have been carried out on glassy carbon and gold electrodes, covered respectively with vacuum deposited and adsorbed transition-metal phthalocyanines. The results show that iron phthalocyanine exhibits a specific catalytic activity for the reduction of molecular oxygen in an acidic aqueous electrolyte. This activity has been related to the occurrence of two metal-centered redox processes in the potential range between oxidation and reduction of the phthalocyanine ligand. The Fe/sup 2 +///sup +/ couple in particular allows for the formation of ..mu..-oxo or ..mu..-peroxo bridges. These bridges are shown to bemore » a prerequisite for the catalytic activity.« less
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